CN103435742A - Hydrophobic POSS (Polyhedral Oligomeric Silsesquioxane)-based hybridization fluorinated acrylate resin as well as preparation method and application thereof - Google Patents
Hydrophobic POSS (Polyhedral Oligomeric Silsesquioxane)-based hybridization fluorinated acrylate resin as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hydrophobic POSS (Polyhedral Oligomeric Silsesquioxane)-based hybridization fluorinated acrylate resin as well as a preparation method and an application thereof. The formula of the hydrophobic POSS-based hybridization fluorinated acrylate resin comprises the following raw materials in percentage by weight: 2-12% of POSS-based monomer, 2-11% of hard monomer, 3-16% of soft monomer, 1.5-7% of fluoroacrylate monomer, 3-11% of crosslinking monomer, 0.4-1.3% of triggering agent and 50-79% of solvent. The application of the hydrophobic POSS-based hybridization fluorinated acrylate resin is characterized in that a crosslinking-type copolymer is mixed with a curing agent, the hydrophobic POSS-based hybridization fluorinated acrylate resin aggregates and is self-assembled in a film-forming solvent so as to form a micellar solution, then a phase isolation technology is used for ensuring that the solvent volatilizes on filter paper or a metal screen to form a film so as to construct a composite multi-scale structure, so that a super-hydrophobic coating is prepared. The preparation method has the advantages that a free radical solution polymerization method is adopted, synthetic conditions are simple, reaction routes are simple, raw materials are simple and easy to get, and the preparation technological processes of organic/inorganic hybrid materials are greatly simplified; the hydrophobic POSS-based hybridization fluorinated acrylate resin has wide application prospect in the field of waterproof and dampproof coating and the like.
Description
Technical field
The present invention relates to a kind of fluorinated acrylate resin, particularly relate to a kind of hydrophobicity POSS base hydridization fluorinated acrylate resin and preparation method thereof and application; The technology of preparing that belongs to organic/inorganic hybridization material.This resin is a kind of fluorinated acrylate super hydrophobic material that contains the polyhedral oligomeric silsesquioxane structure that adopts the free radical solution polymerization reaction method to prepare.
Background technology
Polyhedral oligomeric silsesquioxane (Polyhedral Oligomeric Silsesquioxane is called for short POSS) is a kind of novel nano-material occurred in recent years.Its molecular formula can be expressed as (RSiO
1.5)
n(n generally can be 6,8,10 etc.), the rigidity that it is comprised of with oxygen silicon, the definite nano grade inorganic kernel of structure are the hybrid molecule that shell forms with the organic group R be connected by covalent linkage.Can pass through stronger chemical bonds between it and organic phase, improve the consistency of the two, effectively avoid easy reunion and the weak problem of two-phase interface bonding force of common inorganic particulate.The core of the inorganic cage structure that the Si-O-Si key of POSS forms, have good mechanical property and thermostability.POSS is introduced to traditional polymer, can improve the polymkeric substance use temperature, reduce the polymkeric substance specific inductivity, improve system mechanical property etc.Both at home and abroad to the research of POSS, the overwhelming majority concentrates on by add POSS in system and improves second-order transition temperature, improves decomposition temperature, improves mechanical property, reduces specific inductivity, reduces thermal conductivity etc. at present.The Chinese patent application that publication number is CN102643433A discloses a kind of epoxidation POSS silicone resin and preparation method thereof.The epoxidation silicone resin that this invention makes has high thermal resistance preferably.The Chinese patent application that publication number is CN101139442A discloses containing hybrid resin of silsesquioxane and its production and use.This resin, as the resin matrix of high temperature resistant, wave transparent, radiation hardness matrix material, has excellent normal mechanical behavior under high temperature and good dielectric properties.The Chinese invention patent application of publication number CN102443330A discloses a kind of coated material and preparation method thereof.The coated material of this invention, the resin matrix of the polyhedral oligomeric silsesquioxane POSS that contains hydroxyl and acrylic resin, silicone resin of take makes as raw material.Pencil hardness 3～the 6H of coating, snappiness 1～3mm, shock strength 60～80kg/cm.The Chinese invention patent application that publication number is CN101024751A discloses a kind of coated material containing the POSS acrylate copolymer and preparation method thereof.This coated material can be applicable to woodenware, hardware equipment, optical fiber surface, building material surface and the application of optical storage equipment high surface hardness, and coating hardness is up to pencil hardness 6H.
In prior art, also have by adding POSS to construct hydrophobic surface.The Chinese invention patent application that is CN101029137A as publication number discloses a kind of fluorine-containing POSS acrylate block copolymer resin and synthetic method thereof.This resin adopts atom transfer radical polymerization method (ATRP) synthetic, and after film forming, the contact angle of coating and water is 85～120 °, and wherein POSS is fluorine-containing polyhedral oligomeric silsesquioxane.But the atom transfer radical polymerization method that this invention adopts, process is more loaded down with trivial details, the fluorine-containing POSS preparation technology more complicated of employing, the Static Water contact angle maximum simultaneously reached also only has 120 °.The Chinese invention patent application that publication number is CN103012700A and CN102775567A is all to adopt reversible addition one fragmentation chain transfer free radical polymerization method (RAFT) structure low surface energy, preparation technology's more complicated, and hydrophobic effect is remarkable not.
Summary of the invention
The object of the present invention is to provide a kind of applicable multipolymer second-order transition temperature that has, the hydrophobicity POSS base hydridization fluorinated acrylate resin of resin-bonded excellent performance.
Another object of the present invention is to provide a kind of synthesis condition simple, reaction scheme is short, the preparation method of the hydrophobicity POSS base hydridization fluorinated acrylate resin that raw material is simple and easy to get.
The present invention also has a purpose to be to provide described hydrophobicity POSS base hydridization fluorinated acrylate resin in the hydrophobic or super-hydrophobic application of filming of preparation.
The present invention utilizes the strong self aggregation trend existed between POSS, and assemble self-assembly and form micellar solution in film forming solvent, the recycling phase detachment technique, on filter paper or metal screen, the volatilization film forming is constructed micro-nano coarse structure; Utilize fluorine segment in fluorinated acrylic ester to form low surface energy to the migration of film-Air Interface, comprehensive micro-nano coarse structure and low surface energy material carry out the constructing super-drainage coating simultaneously.The present invention adopts the method for free radical solution polymerization to prepare organic/inorganic hybrid resin (hydrophobicity POSS base hydridization fluorinated acrylate resin), synthesis condition is simple, reaction scheme is short, raw material is simple and easy to get, greatly simplify the preparation flow of organic/inorganic hybridization material, on metal screen, static contact angle reaches more than 150 °.
A kind of hydrophobicity POSS base hydridization fluorinated acrylate resin, by weight percentage, this resin raw material formula is: POSS base monomer accounts for 2～12%, hard monomer accounts for 2～11%, soft monomer accounts for 3～16%, and the fluoroacrylate monomer accounts for 1.5～7%, and cross-linking monomer accounts for 3～11%, initiator accounts for 0.4～1.3%, and solvent accounts for 50～79%;
The structural formula of described POSS base monomer is:
Wherein: R=mono-C
2h
5, a CH
2cH(CH
3) CH
3, a C
6h
5, a C
8h
17,
R'=mono-CH
2(CH
2)
poOCC (CH
3) CH
2; P=2,3 or 4;
Described hard monomer is the just own ester of methyl methacrylate, Tert-butyl Methacrylate, isopropyl methacrylate or methacrylic acid;
Described soft monomer is butyl acrylate, Isooctyl acrylate monomer or ethyl propenoate;
The structural formula of described fluoroacrylate monomer is CF
3(CFX)
m(CH
2)
noOCCYCH
2,; Wherein, X is H, F, F
2or not containing any group; Y is H or CH
3; M=2,5,6,8,10; N=1,2;
Described cross-linking monomer is methacrylic acid-β-hydroxyl ethyl ester, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate or vinylformic acid hydroxy butyl ester;
Described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate;
Described solvent is butylacetate and/or dimethylbenzene
For further realizing the object of the invention, preferably, described POSS base monomer structure formula is: (SiO
1.5)
8r
7(CH
2)
3oOCC (CH
3) CH
2; R=-C wherein
2h
5, R=-CH
2cH (CH
3) CH
3,r=-C
8h
17or R=-C
6h
5.
Or described POSS base monomer structure formula is: (SiO
1.5)
8r
7(CH
2)
4oOCC (CH
3) CH
2or (SiO
1.5)
8r
7(CH
2)
5oOCC (CH
3) CH
2; R=-C wherein
2h
5, R=-CH
2cH (CH
3) CH
3,r=-C
8h
17or
Described fluoroacrylate monomer is trifluoroethyl methacrylate, 2-(perfluoro capryl) ethyl-methyl acrylate, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl esters, vinylformic acid ten trifluoro monooctyl esters, Hexafluorobutyl mathacrylate or vinylformic acid hexafluoro butyl ester.
The preparation method of described hydrophobicity POSS base hydridization fluorinated acrylate resin, comprise the steps:
The first step, join in reactor by the solvent that accounts for solvent quality 29～58% and be heated at 70～110 ℃ of temperature, 0.5～1h refluxes, then by hard monomer, soft monomer, cross-linking monomer, account for initiator quality 40～89% initiator even with the solvent that accounts for solvent quality 5～25%, at the uniform velocity be added drop-wise to reactor in nitrogen atmosphere protection situation in, the control time for adding is 2～3h, and stirring velocity is (300-400) rev/min, drips follow-up continuation of insurance temperature reaction 0.5～4h;
Second step, by the fluoroacrylate monomer, account for initiator quality 9～22% initiator even with the solvent that accounts for solvent quality 5～13%, then at the uniform velocity be added drop-wise in the reaction system of the first step, the control time for adding is 5min～3h, drips rear continuation reaction 0.5～4h;
The 3rd step, POSS base monomer, remaining initiator and remaining solvent is even, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 0.5～3h, drip rear continuation reaction 0.5～4h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin
Described hydrophobicity POSS base hydridization fluorinated acrylate resin is preparing hydrophobic or super-hydrophobic application of filming: POSS base hydridization fluorinated acrylate resin is mixed with film forming solvent, be configured to the solution of 0.1～30% concentration, POSS base hydridization fluorinated acrylate resin is assembled self-assembly in film forming solvent, the micellar solution that the formation median size is 100～800nm, then described micellar solution is mixed with solidifying agent, adopt dip-coating method at stainless steel plate, make one deck uniform coating on filter paper or metal screen, react 1～3h and obtain hydrophobic/super-hydrophobic coat at 20～150 ℃ of temperature,
Described film forming solvent is one or both in Freon 113, dimethylbenzene, toluene, acetone, methyl alcohol, ethanol, trichloromethane, acetonitrile, pimelinketone, hexanaphthene, butylacetate and tetrahydrofuran (THF);
Described solidifying agent is the isocyanates solidifying agent; Count in molar ratio, the NCO/OH in isocyanates solidifying agent and resin is (0.7～1.9): 1.
Described isocyanates solidifying agent is HDI biuret, TDI-HDI tripolymer, HDI tripolymer or IPDI tripolymer.
Coating on described stainless steel plate and the static contact angle of water are 120～140 °, and the coating on described filter paper or metal screen and the static contact angle of water are 145～154 °.
The present invention has following advantage and effect with respect to prior art:
1) POSS base fluorinated acrylate resin of the present invention self-assembly in film forming solvent, recycling solvent evaporates film forming method is prepared the uneven surface of micro nano structure, prepares super-hydrophobic filming, and the Static Water contact angle of filming on metal screen reaches more than 150 °.
2) resin of the present invention adopts hard monomer and soft monomer simultaneously, has applicable multipolymer second-order transition temperature, resin-bonded excellent performance, and what be conducive to film adheres to, and has expanded range of application.
3) POSS base fluorinated acrylate resin of the present invention adopts the preparation of free radical solution polymerization method, and this preparation method's synthesis condition is simple, and reaction scheme is short, and raw material is simple and easy to get, greatly simplifies the preparation flow of organic/inorganic hybridization material.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
The first step, be equipped with electric blender, N
2in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel, add the 11g butylacetate as solvent, be warming up to 85 ℃ of backflow 30min, and pass into N2, then by the 1.9g methyl methacrylate, 2.8g butyl acrylate, 1.9g methacrylic acid-β-hydroxyl ethyl ester, 0.14g join constant pressure funnel after Diisopropyl azodicarboxylate and 4g butylacetate mix, stir with 350 rev/mins of speed, drip off continuously in 2.5h, drip follow-up continuation of insurance temperature reaction 3.5h;
Second step, by 1.4g2-(perfluoro capryl) ethyl-methyl acrylate, join constant pressure funnel after 0.03g Diisopropyl azodicarboxylate and 2g solvent are even, at the uniform velocity be added drop-wise in the reaction system of the first step, 0.5h inside drip off continuously, drip follow-up continuation of insurance temperature reaction 2h;
The 3rd step, by 1.9g POSS(R=mono-CH wherein
2cH(CH
3) CH
3; P=2), 0.04g join in constant pressure funnel after Diisopropyl azodicarboxylate and 8g butylacetate mix, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 1h, drip follow-up continuation of insurance temperature reaction 2h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin;
The 4th step, getting 1g hydrophobicity POSS base hydridization fluorinated acrylate resin mixes with 0.093g HDI tripolymer (N3300), configuration 0.5% concentration resin solution in Freon 113/dimethylbenzene (V/V=1/2) solvent, after mixing, on stainless steel plate, filter paper and metal screen, adopt dip-coating method to film, at 100 ℃ of temperature, reaction 2h makes coating.
Embodiment 2
The first step, in the four-hole boiling flask that electric blender, N2 airway, condensing reflux pipe and constant pressure funnel are housed, add 10g dimethylbenzene as solvent, be warming up to 80 ℃ of backflow 30min, and pass into N2, then by the 1.2g isopropyl methacrylate, 1.7g butyl acrylate, 2.1g Rocryl 410, join constant pressure funnel after 0.1g Diisopropyl azodicarboxylate and 2g solvent are even, stirs with 350 rev/mins of speed, 2.5h inside drip off continuously, drip follow-up continuation of insurance temperature reaction 3h;
Second step, by the 0.9g dodecafluoroheptyl methacrylate, 0.02g Diisopropyl azodicarboxylate and 2g solvent join in constant pressure funnel, at the uniform velocity are added drop-wise in the reaction system of the first step, in 2h, drip off continuously, drip follow-up continuation of insurance temperature reaction 3h;
The 3rd step, get wherein R=mono-CH of 4.1g POSS(
2cH(CH
3) CH
3; P=3), 0.08g join in constant pressure funnel after Diisopropyl azodicarboxylate and 16g solvent are even, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 1h, drip follow-up continuation of insurance temperature reaction 2h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin;
The 4th step, getting 1g hydrophobicity POSS base hydridization fluorinated acrylate resin mixes with 0.089g HDI tripolymer (N3300), configuration 1% concentration resin solution in acetone/hexanaphthene (V/V=2/1) solvent, after mixing, on stainless steel plate, filter paper and metal screen, adopt dip-coating method to film, at 80 ℃ of temperature, reaction 2h makes coating.
Embodiment 3
The first step, in the four-hole boiling flask that electric blender, N2 airway, condensing reflux pipe and constant pressure funnel are housed, add 11g dimethylbenzene as solvent, be warming up to 90 ℃ of backflow 45min, and pass into N2, then by the 2.4g Tert-butyl Methacrylate, 3.6g Isooctyl acrylate monomer, 2.4g the methacrylic acid hydroxy butyl ester, join constant pressure funnel after 0.18g benzoyl peroxide and 4g solvent are even, stirs with 350 rev/mins of speed, 1.5h inside drip off continuously, drip follow-up continuation of insurance temperature reaction 2h;
Second step, by 1.3g methacrylic acid ten trifluoro monooctyl esters, join constant pressure funnel after 0.03g benzoyl peroxide and 2g solvent are even, at the uniform velocity is added drop-wise in the reaction system of the first step, in 1h, drips off continuously, drips follow-up continuation of insurance temperature reaction 1h;
The 3rd step, by 0.1g POSS(R=mono-C wherein
2h
5; P=2), 0.01g join in constant pressure funnel after benzoyl peroxide and 2g solvent are even, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 1.5h, drip follow-up continuation of insurance temperature reaction 2h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin;
The 4th step, getting 1g hydrophobicity POSS base hydridization fluorinated acrylate resin mixes with 0.09g IPDI tripolymer, configuration 2% concentration resin solution in the Freon 113 solvent, after mixing, on stainless steel plate, filter paper and metal screen, adopt dip-coating method to film, at 50 ℃ of temperature, reaction 2h makes coating.
Embodiment 4
The first step, be equipped with electric blender, N
2in the four-hole boiling flask of airway, condensing reflux pipe and constant pressure funnel, add 11g butylacetate/dimethylbenzene (V/V=1/1) as solvent, be warming up to 110 ℃ of backflow 30min, and pass into N2, then by the just own ester of 1.4g methacrylic acid, 2.1g ethyl propenoate, 1.4g Hydroxyethyl acrylate, 0.1g join constant pressure funnel after benzoyl peroxide and 2g solvent are even, stir with 350 rev/mins of speed, drip off continuously in 2.5h, drip follow-up continuation of insurance temperature reaction 3h;
Second step, by the 2g trifluoroethyl methacrylate, the 0.04g benzoyl peroxide, join constant pressure funnel with the 2g solvent after evenly, at the uniform velocity is added drop-wise in the reaction system of the first step, in 5min, drips off continuously, drips follow-up continuation of insurance temperature and react 1h;
The 3rd step, get wherein R=mono-C of 3g POSS(
6h
5; P=2), 0.07g join in constant pressure funnel after benzoyl peroxide and 12g solvent are even, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 2.5h, drip follow-up continuation of insurance temperature reaction 3h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin;
The 4th step, getting 1g hydrophobicity POSS base hydridization fluorinated acrylate resin mixes with 0.1g HDI biuret, configuration 2% concentration resin solution in Freon 113/methyl alcohol (V/V=1/1) solvent, after mixing, on stainless steel plate, filter paper and metal screen, adopt dip-coating method to film, at 80 ℃ of temperature, reaction 2h makes coating.
Embodiment 5
The first step, in the four-hole boiling flask that electric blender, N2 airway, condensing reflux pipe and constant pressure funnel are housed, add the 10g butylacetate as solvent, be warming up to 95 ℃ of backflow 30min, and pass into N2, then by the 2.4g methyl methacrylate, 3.5g Isooctyl acrylate monomer, 1.6g Rocryl 410, join constant pressure funnel after 0.14g Diisopropyl azodicarboxylate and 4g solvent are even, stirs with 350 rev/mins of speed, 1.5h inside drip off continuously, drip follow-up continuation of insurance temperature reaction 2h;
Second step, by 1.5g vinylformic acid hexafluoro butyl ester, join constant pressure funnel after 0.03g Diisopropyl azodicarboxylate and 2g solvent are even, at the uniform velocity is added drop-wise in the reaction system of the first step, in 5min, drips off continuously, drips follow-up continuation of insurance temperature reaction 1h;
The 3rd step, get 1g POSS(wherein
p=4), 0.02g join in constant pressure funnel after Diisopropyl azodicarboxylate and 6g solvent are even, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 1.5h, drip follow-up continuation of insurance temperature reaction 4h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin;
The 4th step, getting 1g hydrophobicity POSS base hydridization fluorinated acrylate resin mixes with 0.09g HDI tripolymer (N3300), configuration 1% concentration resin solution in Freon 113/dimethylbenzene (V/V=1/1) solvent, after mixing, on stainless steel plate, filter paper and metal screen, adopt dip-coating method to film, at 35 ℃ of temperature, reaction 2h makes coating.
Embodiment 6
The OCA mono-40 type contact angle instruments that adopt German Dataphysics company carry out the measurement of Static Water contact angle to the hydrophobicity POSS base hydridization fluorinated acrylate resin coating of embodiment 1～5 preparation, and the situation that records Static Water contact angle on stainless steel plate, filter paper and metal screen is as shown in table 1 below:
Table 1
| Sample | Stainless steel plate ° | Filter paper ° | Metal screen ° |
| Embodiment 1 | 132 | 152 | 154 |
| Embodiment 2 | 127 | 148 | 151 |
| Embodiment 3 | 137 | 149 | 152 |
| Embodiment 4 | 131 | 151 | 149 |
| Embodiment 5 | 138 | 153 | 154 |
As known from Table 1, Static Water contact angle on metal screen and filter paper is than the height on stainless steel plate, reached super-hydrophobicity, this is because the vesicular structure on metal screen and filter paper has all constructed the micron order coarse scale, they and nano level POSS base monomer have constructed micro-nano pair of yardstick coarse structure jointly, while, under the acting in conjunction of the fluorine monomer of low surface energy, films thereby obtained super-hydrophobicity; And on stainless steel plate, single coarse scale also is not enough to construct super-hydrophobicity and films.
Claims (8)
1. a hydrophobicity POSS base hydridization fluorinated acrylate resin, it is characterized in that, by weight percentage, this resin raw material formula consists of: POSS base monomer accounts for 2～12%, and hard monomer accounts for 2～11%, and soft monomer accounts for 3～16%, the fluoroacrylate monomer accounts for 1.5～7%, cross-linking monomer accounts for 3～11%, and initiator accounts for 0.4～1.3%, and solvent accounts for 50～79%;
The structural formula of described POSS base monomer is:
Wherein: R=mono-C
2h
5, a CH
2cH(CH
3) CH
3, a C
6h
5, a C
8h
17or
R'=mono-CH
2(CH
2)
poOCC (CH
3) CH
2; P=2,3 or 4;
Described hard monomer is the just own ester of methyl methacrylate, Tert-butyl Methacrylate, isopropyl methacrylate or methacrylic acid;
Described soft monomer is butyl acrylate, Isooctyl acrylate monomer or ethyl propenoate;
The structural formula of described fluoroacrylate monomer is CF
3(CFX)
m(CH
2)
noOCCYCH
2,; Wherein, X is H, F, F
2or not containing any group; Y is H or CH
3; M=2,5,6,8,10; N=1,2;
Described cross-linking monomer is methacrylic acid-β-hydroxyl ethyl ester, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate or vinylformic acid hydroxy butyl ester;
Described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate;
Described solvent is butylacetate and/or dimethylbenzene.
2. hydrophobicity POSS base hydridization fluorinated acrylate resin according to claim 1, is characterized in that, described POSS base monomer structure formula is: (SiO
1.5)
8r
7(CH
2)
3oOCC (CH
3) CH
2; R=-C wherein
2h
5, R=-CH
2cH (CH
3) CH
3,r=-C
8h
17or R=-C
6h
5.
3. hydrophobicity POSS base hydridization fluorinated acrylate resin according to claim 1, is characterized in that, described POSS base monomer structure formula is: (SiO
1.5)
8r
7(CH
2)
4oOCC (CH
3) CH
2or (SiO
1.5)
8r
7(CH
2)
5oOCC (CH
3) CH
2; R=-C wherein
2h
5, R=-CH
2cH (CH
3) CH
3,r=-C
8h
17or
4. hydrophobicity POSS base hydridization fluorinated acrylate resin according to claim 1, it is characterized in that, described fluoroacrylate monomer is trifluoroethyl methacrylate, 2-(perfluoro capryl) ethyl-methyl acrylate, dodecafluoroheptyl methacrylate, dodecafluorhe-ptylacrylate, methacrylic acid ten trifluoro monooctyl esters, vinylformic acid ten trifluoro monooctyl esters, Hexafluorobutyl mathacrylate or vinylformic acid hexafluoro butyl ester.
5. the preparation method of the described hydrophobicity POSS base of claim 1-4 any one hydridization fluorinated acrylate resin, is characterized in that comprising the steps:
The first step, join in reactor by the solvent that accounts for solvent quality 29～58% and be heated at 70～110 ℃ of temperature, 0.5～1h refluxes, then by hard monomer, soft monomer, cross-linking monomer, account for initiator quality 40～89% initiator even with the solvent that accounts for solvent quality 5～25%, at the uniform velocity be added drop-wise to reactor in nitrogen atmosphere protection situation in, the control time for adding is 2～3h, and stirring velocity is (300-400) rev/min, drips follow-up continuation of insurance temperature reaction 0.5～4h;
Second step, by the fluoroacrylate monomer, account for initiator quality 9～22% initiator even with the solvent that accounts for solvent quality 5～13%, then at the uniform velocity be added drop-wise in the reaction system of the first step, the control time for adding is 5min～3h, drips rear continuation reaction 0.5～4h;
The 3rd step, POSS base monomer, remaining initiator and remaining solvent is even, then at the uniform velocity be added drop-wise in the reaction system of second step, the control time for adding is 0.5～3h, drip rear continuation reaction 0.5～4h, cooling discharge obtains hydrophobicity POSS base hydridization fluorinated acrylate resin.
6. the described hydrophobicity POSS base of claim 1-4 any one hydridization fluorinated acrylate resin is in the hydrophobic or super-hydrophobic application of filming of preparation, it is characterized in that: POSS base hydridization fluorinated acrylate resin is mixed with film forming solvent, be configured to the solution of 0.1～30% concentration, POSS base hydridization fluorinated acrylate resin is assembled self-assembly in film forming solvent, the micellar solution that the formation median size is 100～800nm, then described micellar solution is mixed with solidifying agent, adopt dip-coating method at stainless steel plate, make one deck uniform coating on filter paper or metal screen, react 1～3h and obtain hydrophobic/super-hydrophobic coat at 20～150 ℃ of temperature,
Described film forming solvent is one or both in Freon 113, dimethylbenzene, toluene, acetone, methyl alcohol, ethanol, trichloromethane, acetonitrile, pimelinketone, hexanaphthene, butylacetate and tetrahydrofuran (THF);
Described solidifying agent is the isocyanates solidifying agent; Count in molar ratio, the NCO/OH in isocyanates solidifying agent and resin is (0.7～1.9): 1.
7. hydrophobicity POSS base hydridization fluorinated acrylate resin according to claim 6 is in the hydrophobic or super-hydrophobic application of filming of preparation, and it is characterized in that: described isocyanates solidifying agent is HDI biuret, TDI-HDI tripolymer, HDI tripolymer or IPDI tripolymer.
8. hydrophobicity POSS base hydridization fluorinated acrylate resin according to claim 6 is in the hydrophobic or super-hydrophobic application of filming of preparation, it is characterized in that: the coating on described stainless steel plate and the static contact angle of water are 120～140 °, and the coating on described filter paper or metal screen and the static contact angle of water are 145～154 °.
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|---|---|---|---|
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|---|---|---|---|
| CN201310378783.2A CN103435742B (en) | 2013-08-27 | 2013-08-27 | Hydrophobicity POSS base hydridization fluorinated acrylate resin and preparation method thereof and application |
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Cited By (13)
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| CN105131780A (en) * | 2015-08-28 | 2015-12-09 | 华南理工大学 | POSS-block-containing acrylate copolymer super-hydrophobic coating and preparing method thereof |
| WO2016037403A1 (en) * | 2014-09-11 | 2016-03-17 | 天津大学 | Fluorinated poss composite organosilicon coating, preparation method and anti-icing application |
| CN106215462A (en) * | 2016-08-29 | 2016-12-14 | 华南理工大学 | Super-hydrophobic/super-oleophilic stainless (steel) wire based on POSS base hydridization acrylate coatings and preparation method and application |
| CN106752628A (en) * | 2016-12-13 | 2017-05-31 | 中国人民解放军61489部队 | A kind of building water-proof paint of POSS and silicon oil modified fluorinated acrylate |
| CN108410351A (en) * | 2018-03-09 | 2018-08-17 | 东莞市派乐玛新材料技术开发有限公司 | Organosilicon/inorganic silicon hybridization barrier coat composition and the preparation method and application thereof |
| CN108467504A (en) * | 2018-03-09 | 2018-08-31 | 东莞市派乐玛新材料技术开发有限公司 | A kind of compound barrier film and preparation method thereof with water oxygen barriers function |
| CN108948939A (en) * | 2018-07-10 | 2018-12-07 | 黑龙江泰纳科技发展股份有限公司 | A kind of low-k multifunction electronic protective coating composition |
| CN109704806A (en) * | 2019-03-14 | 2019-05-03 | 湖南辰砾新材料有限公司 | A kind of architectural engineering external-wall heat-insulation material and preparation method thereof |
| CN110746565A (en) * | 2019-10-14 | 2020-02-04 | 苏州联胜化学有限公司 | Washable fluorine-based waterproof agent and preparation method thereof |
| CN110804394A (en) * | 2019-11-12 | 2020-02-18 | 丰县正标卫浴有限公司 | Hydrophobic agent for bathroom board |
| CN111234091A (en) * | 2020-02-21 | 2020-06-05 | 华南理工大学 | POSS (polyhedral oligomeric silsesquioxane) and fluorine-silicon synergistically modified waterborne polyacrylate antifouling resin as well as preparation method and application thereof |
| CN112094588A (en) * | 2020-11-02 | 2020-12-18 | 宁波富纳新材料科技有限公司 | Fingerprint-preventing and anti-glare coating, protective film comprising same and preparation method of protective film |
| CN115537135A (en) * | 2022-10-10 | 2022-12-30 | 广东皇冠新材料科技有限公司 | High-temperature-resistant pressure-sensitive adhesive tape protective film and preparation method thereof |
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| CN101696312A (en) * | 2009-10-27 | 2010-04-21 | 华南理工大学 | Hydrophobic and oleophyllic bi-component acrylic resin and preparation method and application thereof |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016037403A1 (en) * | 2014-09-11 | 2016-03-17 | 天津大学 | Fluorinated poss composite organosilicon coating, preparation method and anti-icing application |
| US9840631B2 (en) | 2014-09-11 | 2017-12-12 | Tianjin University | Polysiloxane/fluorinated POSS hybrid coatings, preparation and anti-icing application thereof |
| CN105131780B (en) * | 2015-08-28 | 2017-06-06 | 华南理工大学 | Acid ester copolymer super-hydrophobic coat of block propylene containing POSS and preparation method thereof |
| CN105131780A (en) * | 2015-08-28 | 2015-12-09 | 华南理工大学 | POSS-block-containing acrylate copolymer super-hydrophobic coating and preparing method thereof |
| CN106215462A (en) * | 2016-08-29 | 2016-12-14 | 华南理工大学 | Super-hydrophobic/super-oleophilic stainless (steel) wire based on POSS base hydridization acrylate coatings and preparation method and application |
| CN106752628A (en) * | 2016-12-13 | 2017-05-31 | 中国人民解放军61489部队 | A kind of building water-proof paint of POSS and silicon oil modified fluorinated acrylate |
| CN108410351B (en) * | 2018-03-09 | 2020-06-16 | 东莞市派乐玛新材料技术开发有限公司 | Organic silicon/inorganic silicon hybrid barrier coating composition and preparation method and application thereof |
| CN108410351A (en) * | 2018-03-09 | 2018-08-17 | 东莞市派乐玛新材料技术开发有限公司 | Organosilicon/inorganic silicon hybridization barrier coat composition and the preparation method and application thereof |
| CN108467504A (en) * | 2018-03-09 | 2018-08-31 | 东莞市派乐玛新材料技术开发有限公司 | A kind of compound barrier film and preparation method thereof with water oxygen barriers function |
| CN108948939A (en) * | 2018-07-10 | 2018-12-07 | 黑龙江泰纳科技发展股份有限公司 | A kind of low-k multifunction electronic protective coating composition |
| CN108948939B (en) * | 2018-07-10 | 2020-04-10 | 黑龙江泰纳科技发展股份有限公司 | Multifunctional electronic protective coating composition with low dielectric constant |
| CN109704806A (en) * | 2019-03-14 | 2019-05-03 | 湖南辰砾新材料有限公司 | A kind of architectural engineering external-wall heat-insulation material and preparation method thereof |
| CN110746565A (en) * | 2019-10-14 | 2020-02-04 | 苏州联胜化学有限公司 | Washable fluorine-based waterproof agent and preparation method thereof |
| CN110804394A (en) * | 2019-11-12 | 2020-02-18 | 丰县正标卫浴有限公司 | Hydrophobic agent for bathroom board |
| CN111234091A (en) * | 2020-02-21 | 2020-06-05 | 华南理工大学 | POSS (polyhedral oligomeric silsesquioxane) and fluorine-silicon synergistically modified waterborne polyacrylate antifouling resin as well as preparation method and application thereof |
| CN112094588A (en) * | 2020-11-02 | 2020-12-18 | 宁波富纳新材料科技有限公司 | Fingerprint-preventing and anti-glare coating, protective film comprising same and preparation method of protective film |
| CN115537135A (en) * | 2022-10-10 | 2022-12-30 | 广东皇冠新材料科技有限公司 | High-temperature-resistant pressure-sensitive adhesive tape protective film and preparation method thereof |
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